Isolation and Crystallographic Characterization of Gd3N@D2(35)-C88 through Non-Chromatographic Methods.

While several nonchromatographic methods are available for the isolation and purification of endohedral fullerenes of the type M3N@Ih-C80, little work has been done that would allow other members of the M3N@C2n family to be isolated with minimal chromatography. Here, we report that Gd3N@D2(35)-C88 can be isolated from the multitude of endohedral and empty cage fullerenes present in carbon soot obtained by electric-arc synthesis using Gd2O3-doped graphite rods. The procedure developed utilizes successive precipitation with the Lewis acids CaCl2 and ZnCl2 followed by treatment with amino-functionalized silica gel. The structure of the product was identified by single-crystal X-ray diffraction.

Isolation of CeLu2 N@Ih -C80 through a Non-Chromatographic, Two-Step Chemical Process and Crystallographic Characterization of the Pyramidalized CeLu2 N within the Icosahedral Cage.

By combining two chemical methods of purification, 4 mg of purified CeLu2 N@C80 was readily isolated from 500 mg of carbon soot extract without the use of recycling HPLC, a method which has previously been necessary to obtain pure samples of endohedral fullerenes. In stage 1, CeLu2 N@C80 was selectively precipitated by virtue of its low first oxidation potential (+0.01 V) and the judicious choice of MgCl2 as the Lewis acid precipitant. For stage 2, we used a stir and filter approach (SAFA), which employed the electron-rich NH2 groups immobilized on silica gel to selectively bind residual endohedrals and higher cage fullerenes that were contaminants from stage 1. Crystallographic analysis of CeLu2 N@C80 in the co-crystal CeLu2 N@Ih -C80 ⋅Ni(octaethylporphyrin)⋅2(toluene) reveals that the Ih -C80 cage is present with a pyramidalized CeLu2 N unit inside.

Tuning the selectivity of Gd3N cluster endohedral metallofullerene reactions with Lewis acids.

We demonstrate the manipulation of the Lewis acid strength to selectively fractionate different types of Gd3N metallofullerenes that are present in complex mixtures. Carbon disulfide is used for all Lewis acid studies. CaCl2 exhibits the lowest reactivity but the highest selectivity by precipitating only those gadolinium metallofullerenes with the lowest first oxidation potentials. ZnCl2 selectively complexes Gd3N@C88 during the first 4 h of reaction. Reaction with ZnCl2 for an additional 7 days permits a selective precipitation of Gd3N@C84 as the dominant endohedral isolated. A third fraction is the filtrate, which possesses Gd3N@C86 and Gd3N@C80 as the two dominant metallofullerenes. The order of increasing reactivity and decreasing selectivity (left to right) is as follows: CaCl2 < ZnCl2 < NiCl2 < MgCl2 < MnCl2 < CuCl2 < WCl4 ≪ WCl6 < ZrCl4 < AlCl3 < FeCl3. As a group, CaCl2, ZnCl2, and NiCl2 are the weakest Lewis acids and have the highest selectivity because of their very low precipitation onsets, which are below +0.19 V (i.e., endohedrals with first oxidation potentials below +0.19 V are precipitated). For CaCl2, the precipitation threshold is estimated at a remarkably low value of +0.06 V. Because most endohedrals possess first oxidation potentials significantly higher than +0.06 V, CaCl2 is especially useful in its ability to precipitate only a select group of gadolinium metallofullerenes. The Lewis acids of intermediate reactivity (i.e., precipitation onsets estimated between +0.19 and +0.4 V) are MgCl2, MnCl2, CuCl2, and WCl4. The strongest Lewis acids (WCl6, ZrCl4, AlCl3, and FeCl3) are the least selective and tend to precipitate the entire family of gadolinium metallofullerenes. Tuning the Lewis acid for a specific type of endohedral should be useful in a nonchromatographic purification method. The ability to control which metallofullerenes are permitted to precipitate and which endohedrals would remain in solution is a key outcome of this work.